How the shift of the glass transition temperature of thin polymer films depends on the adsorption with the substrate

TL;DR

This paper extends a model to explain how the glass transition temperature of thin polymer films varies with substrate interaction, showing it can be controlled by adjusting adsorption strength, with effects quantified by percolation theory.

Contribution

The paper introduces a generalized model for the glass transition temperature shift in thin polymer films, bridging the gap between suspended and strongly adsorbed states, and quantifies the effect of adsorption energy.

Findings

The glass transition temperature shift scales as ^{1/\u03b3_2} with adsorption energy .

Even small adsorption energies ( \, ext{around} \, 0.01 T) increase }T_g.

The increase in }T_g ext{ saturates at high adsorption energies ( \, ext{around} \, 0.5 T).

Abstract

Recent experiments have demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk, the amplitude and the sign of this effect depending on the interaction between the polymer and the substrate. A model has been proposed recently for explaining these effects in two limiting cases: suspended films and strongly adsorbed films. We extend here this model for describing the cross-over between these two situations. We show here how, by adjusting the strength of the adsorption, one can control the glass transition temperature of thin polymer films. In particular, we show that the shift of glass transition temperature, refered to that of a suspended film, varies like $\epsilon^{1/\gamma_2}$ where $\epsilon$ is the adsorption energy per monomer and $\gamma_2$ is the critical exponent for the mass of aggregates in the 2D percolation problem. We show also that the interaction leads to an increase of $T_g$ for $\epsilon$ as small as a few $0.01 T$ where $T$ is the thermal energy, and that this increase saturates at the value corresponding to strongly interacting films for adsorption energies of order $0.5 T$.